Trimethylsilane treatment of dry calcined silica-alumina



United States Patent 3,207,699 TRIMETHYLSELANE TREATMENT OF DRY CALCENED SlLHCA-ALUMHNA William A. Harding, Morton, and Harold Slraiit, Drexel Hill, Pa, assignors to Air Products and Chemicals,

Inc., a corporatien of Delaware No Drawing. Fiied May 4, 1961, Ser. No. 107,645 2 Claims. (Cl. 252-430) This invention concerns porous catalysts and methods of preparation thereof.

Heretofore sorptive solids such as damp silica gel have been treated with dimethyldichlorosilane, which reacted with the moisture film to establish a siliconized, water repellent surface and to improve the tendencies for oil films to form on and in the siliconized silica gel. Heretofore, there have been proposals for conducting chemical reactions in the presence of a catalyst consisting of the combination of a sorptive solid and a gaseous compound of silicon as an accelerator such as silicon tetrachloride.

In accordance with the present invention, an improved acidic catalyst is prepared by chemically attaching a restricted quantity of alkylsilyl groups to the internal surface of an acidic refractory oxide of one or more metals, at an elevated temperature, cooling the treated acidic refractory oxide in an atmosphere containing no oxygen, whereby the catalytic properties of the acidic catalyst are significantly modified without completely destroying the acidity of the catalyst.

The invention is further clarified by reference-to a plurality of examples.

EXAMPLE I An apparatus permitted a gas stream to flow downwardly through several layers of beds of granular particles. All beds were heated externally by a furnace. The uppermost bed and the lowermost bed each consisted of inert granules of fused silica, adapted to heat the gas stream to the temperature of the furnace. The sorptive metal oxide being treated was a 50 ml. bed of granules positioned between the upper and lower beds of inert granules.

After the gas stream flowed downwardly through the three beds, it flowed through three cooling zones to a gas collection container. The gaseous effluent from the furnace was cooled by glass surfaces of three heat exchangers cooled respectively by water, ice, and solid carbon dioxide. Only gases not readily condensed at 80 C. accumulated in the gas collection flasks.

The acidities of refractory oxides have been measured by several procedures. One of the best known ratings for such acidity is the Cat-A activity test described by J. Alexander and H. G. Shimp, National Petroleum News, Aug. 2, 1944, at pages R537 and R538, and Proc. Am. Petroleum Inst. III, 27, 51 (1947). Certain sorptive metal oxides were identified as synthetic silica alumina cracking catalysts having cracking activities expressed as 16, 38, 43 and 65 Cat-A activities, and designated Solids A, B, C and D respectively. Each of said solids A, B, C and D contained 87.5% silica and 12.5% alumina. Solid E was prepared by treating Solid B with aqueous sodium hydroxide and calcining for 2 hours at 760 C., whereby its Cat-A activity was reduced from 38 to 22.9.

Certain silica beads have a relatively large macropore volume by reason of the inclusion of powder in the gelatinous precursor. Such beads having a surface area of 330 m. g. were designated Solid F and those having a surface area of 187 mF/g. were designated Solid G. Fused quartz particles were designated Solid H.

Solid B was heated to 510 C. and treated with trimethylsilane gas (Me SiH) at each of three space rates.

3,207,699 Patented Sept. 21, 1965 The unreacted Me SiH, if any, was caught in the cold traps, and the extent of decomposition was indicated by the volume of uncondensable gas collected. Data concerning the treatment of Solid B with Me siH are shown in Table 1.

Table 1.-Efiect of charge rate on decomposition of Me SiH lVIGsSiH passed over Solid B at 510 0.

Charge rate, Minutes Gas formed, 1. Mmols/min.

There appeared to be good correlation between the charge rate and the initial slope of the curve of gas formation as indicated in Table 2.

The gas formation rate ratios are substantially the same as the charge rate ratios. Such correlation of gas formation rate with the charge rate indicated that during the initial stage of the treatment, the trimethylsilane reacted with the catalyst, bonding the methylsilyl groups to the solid and evolving gases such as hydrogen and methane. Moreover, no silicon-containing product was detected in the efiluent from the reaction chamber during the initial phase of the treatment. From the weight balance, it appeared that the missing elements corresponded substantially to missing --Si(CH groups, although there was some side-reaction decomposition to groups such as (-Si(CH CH (CH Si) involving an Si:C:H ratio of 1:2.5017. Moreover, the concentration of CH, in the gas collection flasks provided supplemental evidence of the extent of decomposition of the -Si(CH groups. The analysis of the silane complexed with the catalyst, as determined by material balance, is indicated in Table 3.

Table 3 Atomic ratios in organosilane uniden- Charge rate titled in material balance (conven- Mmois/min. iently designated as silane complexed with catalyst) Si O H H/C ratio The range from about 0.1 to about 10 mols of silane compound per liter of catalyst is designated as the operable range for the initial reaction with fresh catalyst. The more complicated competition among the several reactions occurs after such initial reaction, and can be readily detected because of the recovery of silicon-containing compounds in the eflluent from the treatment zone after such initial reaction is accomplished.

The catalyst resulting from the treatment of Solid B (87.5% silica, 12.5 alumina, Cat-A activity 38) at 510 C. with about 1 mol of trimethylsilane per liter of silica alumina (for example, charging 4.7 millimols through the described apparatus for about 12 minutes or 2.7 millimols for about 20 minutes or 2.3 millimols per minute for about 42 minutes) has catalytic properties which are distinguishable from the fresh Solid B. For example, the catalyst impregnated with trimethylsilyl groups has remarkable effectiveness as a catalyst for the redistribution reaction of trimethylsilane, whereby trimethylsilane is converted into a mixture of methylsilane, dimethylsilane, trimethylsilane, and tetramethylsilane.

Samples of Solid B were dried at 510 C. and then treated with trimethylsilane at a charge rate of 2.7 millimols per liter for 20 minutes at a series of temperatures. As indicated in Table 4 the treatment at elevated temperatures tends to bring about increased decomposition of the trimethylsilyl group whereby the complex contains fewer methyl groups per silicon atom and whereby more methane gas is formed from the treatment.

Table 4 Atomic ratios in organosilane unidentified in material balance and presumably Tgrgp. deposited in Solid B Si O H H O By a series of tests, a basis is established for setting 100 C. as the minimum temperature and setting 600 C. as the peak temperature for the preparation of the catalyst containing the trimethylsilyl groups.

The silica alumina having Cat-A activity of 38 and designated Solid B was dried for one hour at 510 C. and then treated with trimethylsilane at 277 C. at a rate of 1.1 millimols per minute during the initial period of organosilane deposition and during the subsequent period of disproportionation. Inasmuch as 61.7% of the trimethylsilane underwent redistribution at a temperature as low as 277 0., this sample of catalyst was deemed to be particularly active.

Treatment of silica alumina granules having a Cat-A activity of 65 (designated Solid D) brought about the redistribution of 59.1% of the trimethylsilane passed at the standard conditions subsequent to the deposition of trimethylsilane. However, when the reaction was conducted at 204 instead of 510 C., only 26.9% of the trimethylsilane underwent the redistribution reaction. Under conditions which differed only in that the drying of the 65 Cat-A activity silica alumina (Solid D) was conducted at 204 C. instead of 510 C., only 4.9% of the trimethylsilane underwent the redistribution reaction at 204 C. By a series of tests, a basis was established for the requirement of drying the acidic sorptive solid at conditions at least as severe as one hour at a temperature of 400 C. prior to the initial treatment with the silane to deposit silyl groups at some of the most acidic sites. If the drying of the sorptive acidic solid is insuflicient, the moisture retained at the acidic sites may react with the organosilane instead of the organosilane chemically combining with the sorbtive acidic solid.

4 Sorptive silica beads such as described as F and G have no significant acidity but a relatively high surface area. Trimethylsilane was passed for 18 minutes at a rate of 2.7 mmols/min. over a 50 ml. bed of silica beads F maintained at 510 C. The gas evolution was noted as shown in Table 5.

Table5 Minutes: Liters of gas 4 0.27 8 0.55 10 0.68 12 0.77

In several similar runs the H /CH ratio was significantly higher than it had been in the treatment of cracking catalysts and the data from the initial treatment of silica beads F was as shown in Table 6.

Table 6 Molar ratios (1 fdcomplox Gas formed, Mmols Si C H Hz CH4 H2/CH4 l. 00 2. 77 7. 98 25. 7 8. 4 3. 06 l. 00 2. 84 8. 07 26. 7 6. 7 3. 08 l. 00 2. 85 8. 09 21. 9 4.8 4. 57 l. 00 2. 77 8. 18 25. 4 5. 6 4. 54

Table 7 Minutes: Liters of gas 4 0.23 8 0.49 10 0.57 12 0.60 14 0.62

The molar ratios for the complex added to the solid was 1.00 Si:2.77 C2823 H and 13.9 mmols of H formed during the formation of 7.4 mmols of CH providing a ratio of 1.88. The solid prepared by treating silica beads G with trimethylsilane was not a catalyst in accordance with the present invention because it lacked the significant cracking activity necessary for catalysts of the present invention both before and after treatment with trimethylsilane.

Fused quartz particles (Solid H) were dried at 510 C. and then treated with a trimethylsilane, and the thus treated solid was evaluated as a catalyst for the redistribution reaction of trimethylsilane at 2.7 millimols per minute at 510 C. Most of the trimethylsilane was recovered unchanged, the extent of the redistribution (sometimes called disproportionation) reaction was only 4.2%. Silica beads of larger surface area such as Solids F and G were also relatively poor catalysts. Solid G having a surface area of 187 m. /g., after initial treatment with trimethylsilane, had only enough catalytic artivity to promote 8.6% disproportionation (or redistribution) of additional trimethylsilane. Solid F having a surface area of 330 m. /g., after initial treatment with trimethylsilane, had only enough catalytic activity to promote 14.8% disproportionation of trimethylsilane when the stream of trimethylsilane was continued after the initial deposition of trimethylsilyl groups had been completed at the standard conditions (2.7 millimols per minute at 510 C. after predrying at 510 C.).

had useful properties as a catalyst for the disproportionation of methylsilanes.

EXAMPLE IV The activities of the several trimethylsilylated solids for 5 Sorptive alumina granules were P P F fqllowlng the disproportionation of trimethylsilane are tabulated in thepfocedllfe 0f C0f11 e1111$. 2,809,170, stffllftlng Wlth g T bl punty beta alumma trlhydrate, and obtaining eta alumibl 8 E na granules after calcination. These eta alumina gran- Ta e "2 f3 mama of ules were rehumidified at about 20 C. to contain s-orbed mmet S1 moisture, and designated Solid I. These Solid J granules CONTROL OUTSIDE CO E F PR N INVENTION were treated with trimethylsilane in the apparatus described in Example I. Initially the trimethylsilane was Solid 0 FA Dr 1 Conditions of reaction P went passed at the rate of 2.7 mmols/minute for 17 minutes acgvity 6 weaned at 510 C. over 30.8 g. (50 ml.) of alumina pellets. The 0 233 9 thus treated catalyst was employed as a catalyst for the redistribution reaction of trimethylsilan-e and eventually was regenerated by passage of air over the catalyst. The ND 510 510 2.7 14.8 ND 510 510 27 trimethylsrlane treatment, use and regeneration were reg 352 peated several times. After the fifth regeneration, the catalyst contained 13% silica and 87% alumina, and EXAMPLES OF THE PRESENT INVENTION had a Cat-A act1 v1ty of about 25. The data relating to collection of gas 1s set forth 1n Table 10.

as 510 92 2. 7 11. 9 Table 10 38 510 245 2.7 23.8 as 510 277 1.1 51.7 as 510 510 1.3 59.3 38 510 510 2. 7 56. 7 Liters of gas as 510 510 4.7 53.0 mM Fresh 05 510 204 2.6 20.9 65 510 510 2. 4 59. 1 I II III IV V 0.3 0.3 0.3 0.3 0.3 0.3 EXAMPLE H s 0.75 0.59 0.50 0. 46 0. 43 0. 52

Comparisons are made among catalysts containing the 1g 8- 8- Q45 trimethylsilyl group prepared from Solids A, B and C, 14 1:15 070 0:56 I: I: I: in the apparatus described in connection with Example I. lg Each catalyst was treated with trimethylsilane for 20 minutes at a charge rate of 2.7 millimols per minute at 510 C. The higher the cracking activity of the catalyst, the The data relating to the series are shown in Table 11. greater the decomposition of the trimethylsilane, and the T H fl t lower the hydrogen to carbon ratio in the methylsilyl comable lylsl am regiment of em alumina ponent added to the catalyst. Data relating to the molar ratios of the elements in the methylsilyl component added Molar who complex on Sohd Mmols gas formed to the catalyst are set forth 1n Table 9. Si O H H2 CH4 Table 9 Fresh-- 1.00 2. 31 6.14 19.4 2 i I l'88 3'2; 3%? iii 0 Initial Catalyst Molar ratios of component added to catalyst 1. 00 2. 56 7 11 10- 1 Solid acidity 1. 00 2. 63 7. 63 8. 6 Si O H 13/0 1. 00 2. 68 8. 0O 8. 0

A 10 1. 00 2.50 7. 33 2.93 The catalyst after the fifth regeneration had 13% silica, 2g {88 fig 52g 90 corresponding to 4.6 g. of Si( corresponding to 76.7 mmols of trimethylsilane, which is the same order of I magnitude as the 69 mmols of hydrogen formed during The data of Table 9 indicate that the acidity of the h i t t t Starting material y Sometlmes hall? an effect on the The oxide must be dried at a temperature greater than product obtained by treatment with trimethylsilaue. 400 C. prior t th tre tm with th r anosflane EXAMPLE 111 After the inorganic oxide has been treated with from 0.1 to 10 mols of organosllane per l1ter of Inorganic oxide Sohd E Whlch hijld a acfivfly of and Whlch had and cooled in an atmosphere containing no oxygen to been PWP by lmpregnatlflg Sohd B Wlth excess f l prepare the catalyst of the present invention, the thus ous sodlum hydroxide solution and thereafter calcinlng prepared catalyst may be utilized for of a Variety of for 2 houfs 1400 was dnedu at 510 and then chemical reactions. When used as a catalyst for the disl with trmiethylsllane at 10 at the mm of proportionation of trimethylsilane, the results reported in millimols per mlnute for 10 minutes. The collected gas Table 12 were noted. consisted essentlally of 9.6 millimols of hydrogen and 7.3 Table 12 millimols of methane providing a hydrogen to methane ratio of 1.32:1. In the corresponding treatment of Solid W n t B, for a period of 20 minutes, 17.2 millimols of hydrogen Cami Preheat 5535;}.333 8 p t were formed together with 16.2 millimols of methane pro- Precursor solid activity pviding a hydrogen to methane ratio of 1.06! 1. The cata- C, Mulch/mm lyst complex molar ratio for the sodium oxide deactivated Solid E was 1:2.66:7.79 for the si1icon:carbon:hydrogen J (eta A1203) 90 510 510 2,7 10,2

I (5th 13 ratio instead of 1.00.2.55.7.39 who for the complex de sfjelf t 25 510 510 27 28 9 rived from Solid B. 16 510 510 2.7 24.0

The catalyst prepared by chemically combining trimeth- 510 510 7 2 ylsilyl groups with a sodium oxide deactivated Solid E Obviously many modifications and variations of the invention as hereinbefore set forth may be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.

The invention claimed is:

1. The method of preparing a silica alumina cracking catalyst having modified acidic activity which consists essentially of the steps of: preparing silica alumina granules having cracking activity; drying said granules at a temperature greater than 400 C.; treating the hot dried granules with the vapors of trimethylsilane, whereby hydrogen is evolved and trimethylsilyl groups are bonded to the granules; and cooling the thus treated granules in an atmosphere containing no oxygen, whereby a catalyst is prepared comprising t-rimethylsilyl groups bonded to silica alumina.

2. The method of claim 1 in which the silica alumina granules are prepared to have a cracking activity of at least 15 Cat-A activity; in which the granules are dried at a temperature of at least 400 C. for at least one References Cited by the Examiner UNITED STATES PATENTS 2,486,162 10/49 Hyde 260-4482 2,525,072 10/50 Kearby 117-106 2,722,504 11/55 Fleck 260-4482 X 2,851,473 9/58 Wagner et al 260-4482 3,116,161 12/63 Purnell 260448.2

TOBIAS E. LEVOW, Primary Examiner.

JULIUS GREENWALD, SAMUEL H. BLECH,

Examiners. 

1. THE METHOD OF PREPARING A SILICA ALUMINA CRACKING CATALYST HAVING MODIFIED ACIDIC ACTIVITY WHICH CONSISTS ESSENTIALLY OF THE STEPS OF: PREPARING SILICA ALUMINA GRANULES HAVING CRACKING ACTIVITY; DRYING SAID GRANULES AT A TEMPERATURE GREATER THAN 400*C.; TREATING THE HOT DRIED GRANULES WITH THE VAPORS OF TRIMETHYLSILANE, WHEREBY HYDROGEN IS EVOLVED AND TRIMETHYLSILYL GROUPS ARE BONDED TO THE GRANULES; AND COOLING THE THUS TREATED GRANULES IN AN ATMOSPHERE CONTAINING NO OXYGEN, WHEREBY A CATALYST IS PREPARED COMPRISING TRIMETHYLSILYL GROUPS BONDED TO SILICA ALUMINA. 